Semiconductor device and method for manufacturing the same

ABSTRACT

An object of the present invention is to improve the inter-layer adhesiveness of the diffusion barrier film while maintaining the lower dielectric constant of the diffusion barrier film. A diffusion barrier film for a copper interconnect comprises an insulating material containing silicon, carbon, hydrogen and nitrogen as constituent elements, and also containing Si—H bond, Si—C bond and methylene bond (—CH 2 —). The insulating material involves I 2 /I 1  of not lower than 0.067 and I 3 /I 1  of not higher than 0.0067 appeared in an infrared absorption spectrum; where I 1  is defined as an absorption area of the infrared absorption band having a peak near 810 cm −1 , I 2  is defined as an absorption area of the infrared absorption band having a peak near 2,120 cm −1  and I 3  is defined as an absorption area of the infrared absorption band having a peak near 1,250 cm −1 .

This application is based on Japanese patent application NO. 2003-024350and Japanese patent application NO. 2003-175627, the content of which isincorporated hereinto by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a technology for improving anadhesiveness of an interlayer insulating film employing an insulatingmaterial having a lower dielectric constant.

2. Description of the Related Art

In recent years, for the purpose of satisfying the increasingrequirements for obtaining higher level of the integration ofsemiconductor devices, copper becomes to be widely employed for materialof interconnects or plugs. Copper is a material, which is characterizedin having lower resistance and better electromigration resistance thanthat of aluminum that has been conventionally employed.

Meanwhile, it is known that copper diffuses within an insulating filmcomprising a silicon compound or the like at a higher rate. Thus, whencopper is employed for the interconnect material, it is common that theside surface and the lower surface of the copper interconnect arecovered with a barrier metal and the upper surface thereof is coveredwith a diffusion barrier film. Conventionally, SiN and the like arewidely used for the diffusion barrier film, and recently SiCN havinglower dielectric constant becomes to be often employed in view ofreducing the crosstalk between the interconnects (JP-A-2002-319,619,claim 5 and paragraph 0029).

However, when the diffusion barrier film is formed by using SiCN, theproduction yield of the vias is often reduced, or the adhesivenessbetween the diffusion barrier film and the underlying insulating film isoften deteriorated. These features will be described below in referenceto the annexed figures. FIGS. 1A to 1D show an example of a singledamascene process utilizing SiCN for the diffusion barrier film.

First, a first insulating film 301 and SiO₂ film 302 are deposited insequence on a silicon substrate that includes devices such astransistors formed thereon. These deposited films are partially etchedto form an interconnect trench, and thereafter a barrier metal 303 and acopper film are deposited. Subsequently, chemical mechanical polishing(CMP) processing is carried out to form a copper interconnect 304, sidesurface and bottom surface of which are coated with the barrier metal303. Thereafter, a SiCN film 306, which functions as a diffusion barrierfilm for copper, is formed on the entire surface of the substrate, andthen a second insulating film 308 is deposited thereon. Further, aresist 310 having a predetermined aperture is formed thereon (FIG. 1A).

Subsequently, the second insulating film 308 is partially etched via themask of the resist 310 to form a via hole 312, which extends to thesurface of the SiCN film 306 (FIG. 1B).

Next, the resist 310 is stripped by an oxygen plasma ashing process, andthen etch back processing is conducted to remove the SiCN film 306disposed on the copper interconnect 304 (FIG. 1C).

Thereafter, a barrier metal and a copper film are formed on the entiresurface thereof, and then the portions of the copper film and thebarrier metal outside of the via hole are removed by the CMP processingto form a via plug 320 that is coupled to the copper interconnect 304(FIG. 1D).

However, it is difficult to sufficiently improve the production yieldwhen such process is employed. More specifically, when the resist 310 isstripped off from the multi-layer structure shown in FIG. 1B via theashing process, carbon contained in the SiCN film 306 may react withoxygen contained in the plasma, thereby damaging the SiCN film 306.Although one via hole is shown in FIGS. 1B and 1C, a plurality of viaholes are simultaneously formed on the entire surface of the wafer inthe practical process. Thus, at the stage after the ashing process, thethickness and the condition of the SiCN films 306 disposed on the bottomof the via holes may be different by each of the plurality of the viaholes, resulting in causing over-etching in some of the via holes whenthe SiCN films 306 of the bottom of the via holes are etched off in theprocess shown in FIG. 1C. In the over-etched vias, the surface of thecopper interconnect 304 is exposed to the plasma, and thus the qualityof the copper film may be deteriorated such that the contact resistancewith the via plug 320 is increased.

Also, sufficient adhesiveness between the SiCN film 306 and the SiO₂film 302 overlying thereof may not be obtained, and thus peeling off maybe caused between these layers in the extreme case.

These defects in the contacting nature and the adhesiveness may lead tothe decrease of the production yield and the deterioration of thereliability of the devices.

Meanwhile, an example of evaluating the technology of controlling thequality of the SiCN film is disclosed in the related art. In claim 1,paragraphs 0011, 0012 and 0026 and FIG. 1 of JP-A-2002-83,870, it isdisclosed that, concerning SiCN employed for the etch stop, SiCN etchstop film having better etching selectivity to the underlying film andhaving lower dielectric constant can be obtained by controlling thenumber of functional groups having carbon-hydrogen bond contained in theSiCN film. That is, JP-A-2002-83,870 is directed to solve the technicalproblem occurred in the case where a film corresponding to the SiO₂ film302 of FIGS. 1A to 1D is replaced with a SiCN film (claim 1, paragraphs0011, 0012 and 0026, FIG. 1, or the like of JP-A-2002-83,870). Thus, thedisclosure of JP-A-2002-83,870 provides a guidance for designing theSiCN as the etch stop film, and does not provide an useful informationfor designing the vias or interconnect structures in the case where SiCNis employed for the diffusion barrier film. The diffusion barrier filmthat covers the upper surface of the metal film functions as preventingthe diffusion of metals and further functions as protecting the coppersurface during etching the via holes. Thus, the other view point thanthat of JP-A-2002-83,870 which is related to the etch stop film isnecessary for designing the SiCN film utilizing as the diffusion barrierfilm.

SUMMARY OF THE INVENTION

In view of th above situation, the pr sent invention provides a solutionto the above-mentioned problems, and it is an object of the presentinvention to improve the reliability of the device as well as improvingthe production yield in the case of employing the interconnect structurecomprising a film containing silicon, carbon, hydrogen and nitrogen fora diffusion barrier film disposed on a metal film of an interconnect orplug. More specifically, it is an object of the present invention toimprove the inter-layer adhesiveness of the diffusion barrier film whilemaintaining the lower dielectric constant of the diffusion barrier film.

According to the present invention, there is provided a semiconductordevice comprising: a semiconductor substrate; a metal film formed on thesemiconductor substrate; and a diffusion barrier film covering an uppersurface of the metal film, wherein the diffusion barrier film comprisesan insulating material containing silicon, carbon, hydrogen and nitrogenas constituent elements, and wherein the insulating material containsSi—H bond, Si—C bond and methylene bond (—CH₂—).

The insulating material included in the diffusion barrier film of thepresent invention has a molecular structure having respective chemicalbonds listed above. Since a diffusion barrier film according to thepresent invention contains methylene bond (—CH₂—), improved resistanceto the ashing processing that is conducted in the resist strippingprocess can be provided thereto, thereby effectively inhibiting theproblem of damaging the metal film, which has been described in thedescription of the related art. Since a diffusion barrier film accordingto the present invention contains both methylene bond (—CH₂—) and Si—Hbond, improved adhesiveness thereof with a film disposed thereunder orwith a film disposed thereon can be provided. Since a diffusion barrierfilm according to the present invention contains Si—C bond, thedielectric constant thereof can be effectively reduced.

Here, when the insulating film designed to present an infraredabsorption spectrum thereof, which includes:

I₂/I₁ of not lower than 0.067;

where I₁ is defined as an absorption area of an infrared absorption bandhaving a peak near 810 cm⁻¹; and

I₂ is defined as an absorption area of an infrared absorption bandhaving a peak near 2,120 cm⁻¹, the dielectric constant of the diffusionbarrier film can further surely be reduced.

Also, when the insulating film designed to present an infraredabsorption spectrum thereof, which includes:

I₃/I₁ of not higher than 0.0067;

where I₁ is defined as an absorption area of an infrared absorption bandhaving a peak near 810 cm⁻¹, and

I₃ is defined as an absorption area of an infrared absorption bandhaving a peak near 1,250 cm⁻¹, the adhesiveness of the diffusion barrierfilm with a film disposed thereunder or with a film disposed thereon canbe further improved, and the ability of preventing the diffusion of themetal from the metal film to the interlayer insulating film isconsiderably improved.

The relationship of the above-mentioned I₁, I₂ and I₃ with theproperties of the diffusion barrier film will be fully described laterin the examples. Here, the term “absorption area” appeared in the abovedescription means an area circumscribed with an absorption curve and thebase line in the infrared absorption spectrum. In general, the baselines for the respective infrared absorption bands may be drawn withinthe following range.

I₁: 600–1,220 cm⁻¹;

I₂: 1,900–2,500 cm⁻¹; and

I₃: 1,220–1,300 cm⁻¹.

According to the present invention, there is provided a method formanufacturing a semiconductor device, comprising: forming a firstinsulating film on a semiconductor substrate; selectively removing thefirst insulating film to form an interconnect trench; filling theinterconnect trench with a metal to form a metal film; and depositing adiffusion barrier film including an insulating material containingsilicon, carbon, hydrogen and nitrogen as constituent elements to coverthe upper surface of the metal film, wherein the depositing thediffusion barrier film is conducted by a plasma CVD utilizing a sourcegas containing: (a) trimethylsilane or tetramethylsilane; and (b) anitrogen-containing compound, and wherein a pressure during thedepositing the diffusion barrier film is not higher than 4 Torr.

The manufacturing method having this configuration can provide a stableformation of the diffusion barrier film having lower dielectric constantand improved inter-layer adhesiveness, thereby providing an improvementin the reliability of the devices as well as providing an improvement inthe production yield thereof.

According to the present invention, there is also provided a method formanufacturing a semiconductor device, comprising: forming a firstinsulating film on a semiconductor substrate; selectively removing thefirst insulating film to form an interconnect trench; filling theinterconnect trench with a metal to form a metal film; and depositing adiffusion barrier film including an insulating material containingsilicon, carbon, hydrogen and nitrogen as constituent elements to coverthe upper surface of the metal film, wherein the depositing thediffusion barrier film is conducted by a plasma CVD utilizing a sourcegas containing: (a) vinyl group-containing silane; and (b) anitrogen-containing compound.

The vinyl group-containing silane may contain any one oftrimethylvinylsilane, dimethyldivinylsilane, monomethyltrivinylsilane,or tetravinylsilane.

The manufacturing method having this configuration can provide a furtherstable formation of the diffusion barrier film having lower dielectricconstant and improved inter-layer adhesiveness.

As described above, the present invention has the configuration havingthe SiCN film as the diffusion barrier film disposed on the metal filmhaving a specified structure, and thus semiconductor devices capable ofmanufacturing with improved production yield and having higherreliability are provided.

This summary of the invention does not necessarily describe allnecessary features so that the invention may also be a sub-combinationof these described features.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1D are cross sectional view of a conventional multi-layerinterconnect structure, showing the processing steps of the process forforming the conventional copper interconnect.

FIG. 2 is a cross sectional view of a multi-layer interconnect structureaccording to a preferred embodiment of the present invention.

FIGS. 3A to 3D are cross sectional views of the semiconductor devices,showing the processing steps of the process for forming the copperinterconnect according to the preferred embodiment of the presentinvention.

FIGS. 4E to 4G are cross sectional views of the semiconductor devices,showing the processing steps of the process for forming the copperinterconnect according to the preferred embodiment of the presentinvention.

FIGS. 5H and 5I are cross sectional views of the semiconductor devices,showing the processing steps of the process for forming the copperinterconnect according to the preferred embodiment of the presentinvention.

FIGS. 6J and 6K are cross sectional views of the semiconductor devices,showing the processing steps of the process for forming the copperinterconnect according to the preferred embodiment of the presentinvention.

FIG. 7 is a chemical structure of L-Ox™ having ladder-shaped siloxanehydride structure.

FIG. 8 is a table showing the physical properties of the L-Ox™.

FIG. 9 is a chart of a FT-IR spectrum of the L-Ox™.

FIG. 10 is a graph showing the dependency of the baking condition on thefilm properties of the L-Ox™ film.

FIG. 11 is a molecular skeleton of HSQ.

FIG. 12 is a chart of a FT-IR spectrum of the SiCN film.

FIG. 13 is a chart of a FT-IR spectrum of the SiCN film.

FIG. 14 is a graph showing the dependency of the deposition pressure onthe infrared absorption properties of the SiCN film.

FIG. 15 is a graph showing the dependency of the deposition pressure onthe inter-layer adhesiveness of the SiCN film.

FIG. 16 is a graph showing the dependency of the deposition pressure onthe dielectric constant of the SiCN film.

FIG. 17 is a graph showing the dependency of the flow rate of 3MS on theinfrared absorption properties of the SiCN film.

FIG. 18 is a graph showing the relationship of the infrared absorptionproperties of the SiCN film with the film properties thereof.

FIG. 19 is a cross sectional view of a multi-layer structure forevaluating the barrier properties of the SiCN film.

FIGS. 20A and 20B are graph showing the results of the evaluation of thebarrier properties of the SiCN film.

FIGS. 21A and 21B are graph showing the results of the evaluation of thebarrier properties of the SiCN film.

FIG. 22 is a chart of a FT-IR spectrum of the SiCN film.

FIG. 23 is a cross sectional view of a multi-layer interconnectstructure according to a preferred embodiment of the present invention.

FIG. 24 is a chart of a FT-IR spectrum of the SiCN film.

FIG. 25 is a graph showing results of the evaluations for theelectromigration resistance of the SiCN films prepared in the example.

DETAILED DESCRIPTION OF THE INVENTION

The invention will now be described based on the preferred embodiments.This does not intend to limit the scope of the present invention, butexemplify the invention.

The present invention is more effective when the metal film containscopper as its main constituent. For example, a copper interconnectcontaining an impurity of other element than copper or an interconnectof an alloy of copper and silver may be employed. The metal film of thepresent invention may be obtained by forming a film of metal viaplating, CVD, sputtering or the like, and thereafter processing theformed film of metal as necessary. For example, a metal film, which isprovided as a form of a film embedded in the insulating film may beformed by a damascene processing. The diffusion barrier film accordingto the present invention exhibits a considerable ability of preventingthe diffusion of the metal from the metal film that contains copper asthe main constituent as described above. The metal film constitutes ametal interconnect, an interlayer coupling plug, a pad or the like.

The present invention may include forming an insulating film containingladder-shaped siloxane hydride, being disposed adjacent to the uppersurface of the diffusion barrier film. Ladder-shaped siloxane hydridehas lower dielectric constant and better mechanical stability andchemical stability. Since the present invention employs the diffusionbarrier film having considerably improved adhesiveness withladder-shaped siloxane hydride, better performances of ladder-shapedsiloxane hydride can be fully utilized and the stable layer structurecan be achieved.

Ladder-shaped siloxane hydride is a polymer having a ladder-shapedmolecular structure, and preferably has a dielectric constant of nothigher than 2.9 in view of preventing the interconnect delay, andpreferably has lower film density. For example, the polymer preferablyhas a film density within a range of from 1.50 g/cm³ to 1.58 g/cm³, andhas a refractive index at a wavelength of 633 nm within a range of from1.38 to 1.40. L-Ox™ or the like may be illustrated as a typical filmmaterial.

FIG. 7 shows a chemical structure of the L-Ox™, which has ladder-shapedsiloxane hydride structure. The sign “n” appeared in the structureindicates a positive number of equal to or greater than 1. FIG. 8 showsphysical properties of the L-Ox™ having such chemical structure.

It was confirmed by the results of the FT-IR measurement shown in FIG. 9that the L-Ox™ has the chemical structure shown in FIG. 7. Thecharacteristic feature found in the chart of FIG. 9 is a sharp peakappeared at about 830 cm⁻¹ indicating the presence of Si—H bond, and therapid ascent of the peak suggests that the L-Ox™ has a two-dimensionalchemical structure. Also, an expected another peak indicating thepresence of Si—H bond, which is expected to appear at a higher wavenumber side around approximately 870 cm⁻, is extremely small, and thusthis also indicates that the material to be measured has thetwo-dimensional chemical structure.

The physical properties of the L-Ox™ are also variable depending on thebaking temperature. This will be described on the basis of thedisclosure of FIG. 10.

The L-Ox™ formed by baking within the inert gas atmosphere such asnitrogen or the like at a temperature within a range of from 200 degreeC. to 400 degree C. has the following properties. In FIG. 10, “R.I.”indicates the refractive index at a wavelength of 633 nm. The refractiveindex is a parameter that has an influence directly on the dielectricconstant, and the value thereof varies within a range of from 1.38 to1.40. The values of the refractive indexes thereof at a temperaturelower than 200 degree C. or at a temperature higher than 400 degree C.were higher than 1.40.

The densities of the L-Ox™ formed by baking at a temperature from 200degree C. to 400 degree C. were 1.50 g/cm³ to 1.58 g/cm³. The density ofthe film baked at a temperature higher than 400 degree C. was higherthan 1.60 g/cm³. The density of the film baked at a temperature lowerthan 200 degree C. was not measurable.

When the film was formed by baking at a temperature lower than 200degree C., a peak appeared at about 3,650 cm⁻¹, which is thought toindicate the presence of Si—OH (silanol) bonding, was observed in theFT-IR spectrum. The film baked at a temperature of higher than 400degree C. exhibited a noticeable increase of the density.

The above results indicate that the L-Ox™ having better properties aswell as having lower dielectric constant can be stably obtained bybaking at an atmosphere temperature from 200 degree C. to 400 degree C.when th insulating film including the L-Ox™ is deposited.

FIG. 11 shows a molecular skeleton of conventionally known hydrogensilsesquioxane (HSQ) having siloxane hydride structure that is athree-dimensional chemical structure. (This is cited from “SemiconductorTechnology Outlook”, 1998, pp. 431–435.) The sign “n” is a positivenumber equal to or higher than 1.

The two materials having the above described structures haveconsiderably different film stabilities during the manufacturingprocesses, and the L-Ox™ exhibits markedly superior film stability toHSQ. It is considered that this is because the decrease of Si—H contentin L-Ox™ during the manufacturing process is lower than that in HSQ. Itis also considered that the difference in the manner of forming bondswith hydrogen atoms is also a reason thereof. More specifically, in HSQ,hydrogen atom is bonded thereto at a corner of the cubic structure, andmeanwhile in L-Ox™, hydrogen atom is bonded thereto at a portion of theside of the ladder structure. Therefore, the density around hydrogenatoms of HSQ is lower than that of L-Ox™, and thus it is considered thathydrogen bond included in HSQ is more reactive than hydrogen bondincluded in L-Ox^(TR) for the structural reason.

Although the present invention has been described by way of exemplaryembodiments, it should be understood that many changes and substitutionsmay be made by those skilled in the art without departing from thespirit and the scope of the present invention which is defined only bythe appended claims.

EXAMPLES

The preferable embodiments according to the present invention will bedescribed with reference to Examples.

(Infrared Absorption Spectrum for SiCN Film)

Before describing the Examples, the infrared absorption spectrum forSiCN film will be described on the basis of the data.

FIG. 12 is a chart of FT-IR spectrum of SiCN film. Attributions ofrespective absorption bands are shown in the chart. In the Examplesdescribed later, an absorption area of an absorption band was obtainedby drawing a base line shown in the cart, and calculating an areacircumscribed with an absorption curve and the base line to provide theabsorption area. Here, the term “absorption area” means an areacircumscribed with the absorption curve and the base line in theinfrared absorption spectrum.

-   (i) Infrared absorption band having a peak near wave number of 810    cm⁻¹;    Si—C bond;    The absorption area of this absorption band is designated as I₁.-   (ii) Infrared absorption band having a peak near wave number of    2,120 cm⁻¹;    Si—H bond;    The absorption area of this absorption band is designated as I₂.-   (iii) Infrared absorption band having a peak near wave number of    1,250 cm⁻¹;    Si—CH₃. bond;    The absorption area of this absorption band is designated as I₃.

The base lines for the respective infrared absorption bands may begenerally drawn within the following range.

I₁: 600–1,220 cm⁻¹;

I₂: 1,900–2,500 cm⁻¹; and

I₃: 1,220–1,300 cm⁻¹.

FIG. 13 is an enlarged view of the absorption spectrum from the wavenumber of 3,500 cm⁻¹ to 2,500 cm⁻¹. It is seen that an absorbing bandindicating the presence of methyl bond (—CH₃) appears in a higher-wavenumber side and an absorbing band indicating the presence of methylenebond (—CH₂—) appears in a lower-wave number side.

Example 1

In the present example, the influence of the pressure for depositingSiCN film on the infrared absorption profile of deposited films wasevaluated by depositing SiCN films at different deposition pressures. Inthe present example, a silicon oxide film was deposited on a siliconsubstrate, and thereafter SiCN was deposited thereon via a plasma CVD. Aparallel plate plasma CVD apparatus was employed for the depositionapparatus. The conditions for the deposition process were as follows.

-   (a) Volumetric flow rate of source gas:-   trimethylsilane (3MS) 150 sccm;-   ammonia 300 sccm; and-   helium 300 sccm;-   (b) plasma power: 300 W; and-   (c) deposition chamber pressure: 3 to 5 Torr.

Absorption areas for Si—C bond, Si—H bond and Si—CH₃ bond were measuredfor the respective deposited films. The measured absorption areas forSi—C bond, Si—H bond and Si—CH₃ bond were designated as I₁, I₂ and I₃,respectively, and the values of I₂/I₁ (Si—H bond/Si—C bond) and I₃/I₁(Si—CH₃ bond/Si—C bond) were evaluated on the basis of the measuredareas.

Further, the adhesiveness between the SiCN film and a silicon oxide filmdeposited on the SiCN film was evaluated by conducting a tape peelingtest. More specifically, grooves having a lattice pattern were createdon the SiCN film and the silicon oxide film was divided by using acutter blade to separate them into a plurality of rectangular regions.Then, adhesive tape was posted on the surface of the SiCN film. The tapewas pulled toward a predetermined direction, and the number of therectangular regions, in which the peeling off was occurred on the SiCN,was counted. Determinations for the results of the evaluation were made:the sign “X” was presented if any peeling off was occurred, and the sign“O” was presented where no peeling of was occurred.

The test results are shown in FIGS. 14 and 15. In the table of FIG. 15,“Adhesion” indicates the results of the evaluation. Also, the sign “<”appeared in the column of “CH₃:CH₂” indicates that the absorption areafor CH₂ (methylene bond) is larger than the absorption are for CH₃(methyl bond) in the chart of FIG. 13, and the sign “>” indicates viceversa.

As seen in FIG. 14, it is found that the absorption area ratios of theabove-mentioned absorption bands significantly depend on the depositionpressure. As seen in FIG. 15, it is also found that better adhesivenessis obtainable by having a pressure within a range of from 3 to 4 Torr.

Next, films were deposited under the deposition conditions similar tothe above-mentioned conditions except that the different depositionpressure was selected for the respective films from a range of from 2 to5 Torr, and the dielectric constants (at 1 MHz) of the deposited filmswere measured. The results are shown in FIG. 16. It is found that thedielectric constant strongly depends on the pressure, and that higherpressure provides lower dielectric constant as long as the depositionpressure range of the present example is concerned.

Here, the ratios of the absorption areas of the above-mentionedabsorption bands also strongly depend on other deposition conditions inaddition to the deposition pressure. FIG. 17 is a graph showing theresults of measured values of I₂/I₁ (Si—H bond/Si—C bond) and I₃/I₁(Si—CH₃ bond/Si—C bond) of the obtained films that were deposited bychanging the flow rate of the trimethylsilane contained in the sourcegas.

As seen in the results shown in FIG. 17, it is found that, concerningthe flow rate of the trimethylsilane contained in the source gas, thequantity of Si—CH₃ bond drastically increases when the selected flowrate thereof exceeds a certain value. When the volumetric flow rate oftrimethylsilane was selected to 120 sccm, both of the quantities of Si—Hand CH₃ decreased and dielectric constant of not lower than 5.0 wasexhibited.

Example 2

In this example, various samples comprising SiCN films having variousinfrared absorption profiles were prepared by variously selecting theabove-mentioned deposition conditions (a) to (c). Similarly as in theExample 1, SiCN film was deposited on the silicon oxide film formed onthe silicon substrate.

The dielectric constant and the adhesiveness with the silicon oxide filmwere evaluated for the obtained samples. The results are shown in FIG.18. When a larger quantity of Si—CH₃ bond was contained and I₃/I₁(Si—CH₃ bond/Si—C bond) was higher than 0.0067, a defect in theadhesiveness was occurred. When smaller quantity of Si—H bond wascontained and I₂/I₁ (Si—H bond/Si—C bond) was not greater than 0.067,the relative dielectric constant thereof was not smaller than 5.0. Thus,it is found from the above evaluations that both the adhesiveness andthe dielectric constant can be better if:I₃/I₁ (Si—CH₃ bond/Si—C bond) is not greater than 0.0067; andI₂/I₁ (Si—H bond/Si—C bond) is not smaller than 0.067.

It is also found from the figure that the region indicating that thecontents of CH₂ bond is larger than the contents of CH₃ bond overlapsthe region in which I₃/I₁ (Si—CH₃ bond/Si—C bond) is not greater than0.007.

Example 3

Two samples having a structure shown in FIG. 19 were prepared indifferent conditions for depositing the SiCN film, and the differencetherebetween in the barrier performances to the thermal diffusion ofcopper were evaluated.

The deposition conditions for preparing the sample 1 were as follows.

-   (a) Volumetric flow rate of source gas:-   trimethylsilane (3MS) 150 sccm;-   ammonia 300 sccm; and-   helium 300 sccm;-   (b) plasma power: 300 W; and-   (c) deposition chamber pressure: 3 Torr.

The deposition conditions for preparing the sample 2 were as follows.

-   (a) Volumetric flow rate of source gas:-   trimethylsilane (3MS) 150 sccm;-   ammonia 300 sccm; and-   helium 300 sccm;-   (b) plasma power: 300 W; and-   (c) deposition chamber pressure: 5 Torr.

The infrared absorption spectrums of the obtained films were measured,and the results were as follows.I ₂ /I ₁ (Si—H bond/Si—C bond)=0.074; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)=0.004.  Sample 1:I ₂ /I ₁ (Si—H bond/Si—C bond)=0.070; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)=0.0095.  Sample 2:

The barrier properties to the thermal diffusion of copper were evaluatedfor these samples. More specifically, the statuses for the distributionof Si and Cu were measured by secondary ion mass spectrometry (SIMS) forthe film just after the deposition (i.e., film as deposited) and for thefilm after experiencing 10 cycles of the thermal processing at 400degree C. for 30 minutes. The results are shown in FIGS. 20A, 20B, 21Aand 21B. FIGS. 20A and 20B are the results of the evaluation forsample 1. No significant difference in the status of elements existingin the film was seen between the thermally processed film and the filmas deposited. FIGS. 21A and 21B are the results of the evaluation forsample 2. It was seen that the concentration of copper in the SiCN filmincreased by the thermal processing. Thus, it was found that copperdiffused into the SiCN in the sample 2.

The difference in the barrier performance to the diffusion of Cu can berepresented in relation to the ratio of CH₂ bond to CH₃ bond. It isconsidered that larger content of CH₂ bond provides higher density,thereby inhibiting the diffusion of Cu atom.

Example 4

The present example shows an example, in which the present invention wasapplied to a dual-layer copper interconnect having a single damascenestructure. The present example employed a film called L-Ox™, which is aladder-shaped siloxane hydride. FIG. 2 is a cross sectional view ofstructure of a semiconductor device according to the present example.The semiconductor device according to the present example has aconfiguration, in which a lower interconnect comprising a Cu film 209 iscoupled to an upper interconnect comprising a Cu film 223 through acopper plug 228.

The lower interconnect comprising the Cu film 209 is formed inmultilayer films that include an underlying insulating film 201, a SiCNfilm 202, a L-Ox™ film 203 and a SiO₂ film 204. A side surface and abottom surface of the Cu film 209 are covered by Ta/TaN films 208.

The copper plug 228 is provided in a hole formed in multilayer filmscomprising a SiCN film 211 disposed on the SiO₂ film 204 and a SiO₂ film212. A side surface and a bottom surface of the hole are covered byTa/TaN films 226.

The upper interconnect comprising the Cu film 223 is formed inmultilayer films comprising a SiCN film 213, L-Ox™ film 216 and a SiO₂film 217. A side surface and a bottom surface of the Cu film 223 arecovered by Ta/TaN films 220, and a SiCN film 222 is formed to cover anupper surface thereof.

Next, the method for manufacturing the semiconductor device according tothe present example will be described. FIGS. 3A to 3D, 4E to 4G, 5H and5I, 6J and 6K are cross sectional views of a semiconductor device,showing the processing steps for manufacturing the semiconductor deviceaccording to the preferred example.

First, a multilayer structure shown in FIG. 3A was formed. An underlyinginsulating film 201 was disposed on a substrate (not shown) having asemiconductor device formed thereon, and a SiCN film 202, which would bean etch stop film at the stage of forming an interconnect trench, wasdeposited via the plasma CVD thereon to a thickness of 50 nm. Then, aL-Ox™ film 203 was formed by an applying method to a thickness of 300nm, and the baking processing was carried out within N₂ atmosphere at400 degree C. for 30 minutes. Subsequently, a SiO₂ film 204 wasdeposited via the plasma CVD to a thickness of 100 nm. Thereafter, theSiO₂ film 204 and the L-Ox™ film 203 were selectively dry-etched to forman interconnect trench 207.

Subsequently, Ta/TaN films 208 and a Cu film 209 were formed to fill theinterconnect trench therewith, thereby forming an interconnect. Then, aSiCN film 211 and a SiO₂ film 212 were deposited in sequence on theentire surface of the substrate to cover the interconnect. Thedeposition of the SiCN film 211 was carried out by the plasma CVD, andthe process conditions thereof were as follows.

-   (a) Volumetric flow rate of source gas:-   trimethylsilane (3MS) 150 sccm;-   ammonia 300 sccm; and-   helium 300 sccm;-   (b) plasma power: 300 W; and-   (c) deposition chamber pressure: 3.3 Torr.

Here, the infrared absorption spectrum of a SiCN film, which wasdeposited on a substrate by a process under the conditions same as thosefor depositing the above described SiCN film 211, was measured, and theresult was as follows.I ₂ /I ₁ (Si—H bond/Si—C bond)=0.077; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)=0.005.

As described above, the layer structure shown in FIG. 3A was obtained.

Then, an anti-reflective film 250 and a photo resist 214 were applied onthe deposited SiO₂ film 212, and a resist pattern for vias was formedvia a photolithography technique (FIG. 3B).

Further, the SiO₂ film 212 was etched through the resist pattern forvias by a dry etching technique to form a pattern for vias. Thereafter,ashing process was carried out to strip the photo resist 214 and theanti-reflective film 250 (FIG. 3C). Next, the SiCN film 211 disposed onthe bottom of the via was etched back, and the etch residue was strippedwith a stripping solution (FIG. 3D).

Thereafter, a Ta/TaN films 226 having a thickness of 30 nm was depositedvia sputtering process, and a Cu film (not shown) for a seed was formedthereon, and after that, a Cu film 227 was formed to a thickness of 700nm via the electrolytic plating process to fill the via patterntherewith. Thereafter, a thermal processing was carried out at 400degree C. for the crystallization (FIG. 4E).

Then, the Cu film 227 and the Ta/TaN films 226 on the SiO₂ film 212 wereremoved by the CMP process (FIG. 4F).

Then, a copper plug 228 was formed by a process same as that employed inthe formation of the lower interconnect and a SiCN film 213, which willbe a second Cu-diffusion barrier film, was formed to a thickness of 50nm (FIG. 4G).

Then, a L-Ox™ film 216, which functions as a second interlayerinsulating film, was applied and baked to a thickness of 300 nm, andthen a SiO₂ film 217 was deposited thereon to a thickness of 100 nm.Next, an anti-reflective film 250 and a photo resist 218 were appliedthereon, and an aperture was formed in the photo resist 218 via aphotolithography technique (FIG. 5H).

Then, the SiO₂ film 217 and the L-Ox™ film 216, which were theinterlayer insulating film for the second interconnect, were etched viathe mask of the photo resist 218. Then, ashing process was carried outto strip the photo resist 218 and the anti-reflective film 250. Then,the etch back process for the entire surface was carried out to removethe SiCN film 213 of the Cu-diffusion barrier film. Then, the etchresidue was stripped with a stripping solution (FIG. 5I).

Thereafter, Ta/TaN films 220 were deposited to a thickness of 30 nm viathe sputtering process, and a Cu film (not shown) for a seed was formedon the Ta/TaN films 220 to a thickness of 100 nm. Then, a Cu film 221was formed thereon to a thickness of 700 nm via the electrolytic platingprocess, and after that, CMP processing was conducted to form the upperinterconnect (FIG. 6J).

Then, after removing benzotriazole (BTA) layer, a SiCN film 222 of aCu-diffusion barrier film was formed thereon to a film thickness of 50nm (FIG. 6K). As described above, the copper multilayer interconnecthaving the single damascene structure shown in FIG. 2 was formed.Thereafter, a procedure substantially similar to the above describedprocess was employed to form an upper interconnect to manufacture asemiconductor device having 9 interconnect layers. The semiconductordevices were obtained with higher production yield, and the obtainedsemiconductor devices had better reliability.

Example 5

The present example illustrates an example of employingtrimethylvinylsilane, ammonia and helium gases for a source materialsfor depositing a SiCN film of a diffusion barrier film.

The employed deposition apparatus was the parallel plate plasma CVDapparatus as in the former examples. The conditions for the depositionprocess were as follows.

-   (a) Volumetric flow rate of source gas:-   trimethylvinylsilane (TMVS) 150 sccm;-   ammonia 300 sccm; and-   helium 300 sccm;-   (b) plasma power: 300 W; and-   (c) deposition chamber pressure: 3 Torr.

The infrared absorption spectrum of the obtained films is as shown inFIG. 22. The results of the measurements were obtained as follows.I ₂ /I ₁ (Si—H bond/Si—C bond)=0.069; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)=0.0059.

Further, it is also found that the relative dielectric constant of theobtained film was about 4.0, and thus these deposition conditions iscapable of providing a reduced dielectric constant in comparison withthe case employing 3MS.

A dual-layer copper interconnect having a single damascene structure wasformed by utilizing such film. The interconnect insulating film employedin this example was a SiOCH film, which is a film having lowerdielectric constant (relative dielectric constant=2.9). FIG. 23 is across sectional view showing the structure of a semiconductor deviceaccording to the present example.

The semiconductor device according to the present example has aconfiguration, in which a lower interconnect comprising a Cu film 209 iscoupled to an upper interconnect comprising a Cu film 223 through acopper plug 228.

The lower interconnect comprising the Cu film 209 is formed inmultilayer films that include an underlying insulating film 201, a SiCNfilm 502, a SiOCH film 503 and a SiO₂ film 204. A side surface and abottom surface of the Cu film 209 are covered with Ta/TaN films 208.

The copper plug 228 is provided in a hole formed in multilayer films,which is disposed on the SiO2 film 204 and comprises a SiCN film 511,SiOCH film 512 and a SiO₂ film 510. A side surface and a bottom surfaceof the hole are covered by Ta/TaN films 226.

The upper interconnect comprising the Cu film 223 is formed inmultilayer films comprising a SiCN film 513, a SiOCH film 516 and a SiO₂film 217. A side surface and a bottom surface of the Cu film 223 arecovered by Ta/TaN films 220, and a SiCN film 222 is formed to cover anupper surface thereof.

A cover structure was formed for the obtained layer structure, andelectromigration characteristics thereof was evaluated. As a comparativeexample, a sample comprising SiCN film being manufactured by using 3MSgas and having an infrared absorption spectrum shown in FIG. 24 was alsopresented. The spectrum shown in FIG. 24 provides the following resultfor the SiCN film of the comparative sample:I2/I1 (Si—H bond/Si—C bond)=0.055; andI3/I1 (Si—CH₃ bond/Si—C bond)=0.0090.That is, such film for the comparative sample is applicable in thecriteria described before in relation to the failure of the operation ofthe device, i.e.,I ₂ /I ₁ (Si—H bond/Si—C bond)<0.067; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)>0.0067.

FIG. 25 shows results of evaluations of the lectromigration resistancefor two types of samples having each of the above-mentioned two types ofSiCN films. Sample 1 includes the SiCN film deposited by usingtrimethylvinylsilane (TMVS), and sample 2 includes the SiCN filmdeposited by using trimethylsilane (3MS). The electromigrationcharacteristics of the sample 1, which includes the SiCN film depositedby using TMVS, was improved with five folds or higher, compared to thatof the comparative sample 2, which includes the SiCN film deposited byusing 3MS. It is considered that the reason is that the ratio of theabsorption areas of the sample 1 having SiCN film deposited by usingTMVS satisfies the criteria for obtaining better adhesiveness and lowerdielectric constant described in the example 2, that is:I ₂ /I ₁ (Si—H bond/Si—C bond)>0.067; andI ₃ /I ₁ (Si—CH₃ bond/Si—C bond)<0.0067,and that the SiCN film included in the comparative sample 2 does notsatisfy the criteria.

It is supposed that the SiCN film has an improved adhesiveness with theCu film by having increased Si—H and reduced Si—CH₃, and thus theimprovement in the electromigration characteristics thereof is achieved.

Although the examples are described in relation to the cases employingTMVS, other compounds may be employed as long as the compound containsvinyl group, and the exemplary compounds for obtaining similar resultsto those using TMVS may be dimethyldivinylsilane,monomethyltrivinylsilane or tetravinylsilane.

Although the present invention is described with respect to thepreferred embodiments, it should be understood that the disclosurescontained herein are by way of illustration only, and optionally theconfiguration and/or the process thereof may be partially substitutedwith other configuration and/or process.

For example, although the copper interconnect is employed in the abovedescribed preferred examples, the interconnect may also be a copperalloy interconnect, which is formed of an alloy of copper with at leastone different element selected from the group consisting of: Al(aluminum); Ag (silver); W (tungsten); Mg (magnesium); Be (beryllium);Zn (zinc); Pd (palladium); Cd (cadmium); Au (gold); Hg (mercury); Pt(platinum); Zr (zirconium); Ti (titanium); Sn (tin); Ni (nickel); Nd(neodymium); and Fe (iron).

Although the Ta/TaN films are employed for the barrier metal in theabove disclosures of the examples, the present invention may have aconfiguration, in which the barrier metal comprises at least oneselected from the group consisting of: Ti; TiN; TiSiN; Ta; TaN; andTaSiN.

1. A semiconductor device, comprising: a semiconductor substrate; ametal film disposed on said semiconductor substrate; and a diffusionbarrier film covering an upper surface of said metal film, wherein saiddiffusion barrier film comprises an insulating material containingsilicon, carbon, hydrogen and nitrogen as constituent elements, andwherein said insulating material contains Si—H bond, Si—C bond andmethylene bond (—CH₂—).
 2. The semiconductor device as set forth inclaim 1, wherein an infrared absorption spectrum of said insulatingmaterial includes: I₂/I₁ of not lower than 0.067; where I₁ is defined asan absorption area of an infrared absorption band having a peak near 810cm⁻¹, and I₂ is defined as an absorption area of an infrared absorptionband having a peak near 2,120 cm⁻¹.
 3. The semiconductor device as setforth in claim 1, wherein an infrared absorption spectrum of saidinsulating material includes: I₃/I₁ of not higher than 0.0067; where I₁is defined as an absorption area of an infrared absorption band having apeak near 810 cm⁻¹, and I₃ is defined as an absorption area of aninfrared absorption band having a peak near 1,250 cm⁻¹.
 4. Thesemiconductor device as set forth in claim 2, wherein an infraredabsorption spectrum of said insulating material includes: I₃/I₁ of nothigher than 0.0067; where I₁ is defined as an absorption area of aninfrared absorption band having a peak near 810 cm⁻¹, and I₃ is definedas an absorption area of an infrared absorption band having a peak near1,250 cm⁻¹.
 5. The semiconductor device as set forth in claim 1, whereinsaid metal film contains copper as a main constituent.
 6. Thesemiconductor device as set forth in claim 2, wherein said metal filmcontains copper as a main constituent.
 7. The semiconductor device asset forth in claim 3, wherein said metal film contains copper as a mainconstituent.
 8. The semiconductor device as set forth in claim 4,wherein said metal film contains copper as a main constituent.
 9. Asemiconductor device, comprising: a semiconductor substrate; a metalfilm disposed on said semiconductor substrate; and a diffusion barrierfilm covering an upper surface of said metal film, wherein saiddiffusion barrier film comprises an insulating material containingsilicon, carbon, hydrogen and nitrogen as constituent elements, andwherein said insulating material contains Si—H bond, Si—C bond andmethylene bond (—CH₂—), wherein said diffusion barrier film includes acontrolled quantity of said Si—H bond such that a dielectric constant ofsaid diffusion baffler film is less than 5.0.
 10. The semiconductordevice as set forth in claim 9, wherein an infrared absorption spectrumof said insulating material includes: I₂/I₁ of not lower than 0.067;where I₁ is defined as an absorption area of an infrared absorption bandhaving a peak near 810 cm⁻¹, and I₂ is defined as an absorption area ofan infrared absorption band having a peak near 2,120 cm⁻¹.
 11. Thesemiconductor device as set forth in claim 9, wherein an infraredabsorption spectrum of said insulating material includes: I₃/I₁ of nothigher than 0.0067; where I₁ is defined as an absorption area of aninfrared absorption band having a peak near 810 cm⁻¹, and I₃ is definedas an absorption area of an infrared absorption band having a peak near1,250 cm⁻¹.
 12. The semiconductor device as set forth in claim 10,wherein an infrared absorption spectrum of said insulating materialincludes: I₃/I₁ of not higher than 0.0067; where I₁ is defined as anabsorption area of an infrared absorption band having a peak near 810cm⁻¹, and I₃ is defined as an absorption area of an infrared absorptionband having a peak near 1,250 cm⁻¹.
 13. The semiconductor device as setforth in claim 9, wherein said metal film contains copper as a mainconstituent.
 14. The semiconductor device as set forth in claim 10,wherein said metal film contains copper as a main constituent.
 15. Thesemiconductor device as set forth in claim 11, wherein said metal filmcontains copper as a main constituent.
 16. The semiconductor device asset forth in claim 12, wherein said metal film contains copper as a mainconstituent.